Chitosan oligosaccharide cross-linked polymer as well as preparation method and application thereof

Abstract

The invention provides a chitosan oligosaccharide cross-linked polymer, the chitosan oligosaccharide cross-linked polymer at least contains chitosan oligosaccharide, sodium carboxymethyl cellulose and organic acid monovalent metal salt, and the chitosan oligosaccharide cross-linked polymer is at least formed by cross-linking through physical action between amino in the chitosan oligosaccharide and carboxyl in the sodium carboxymethyl cellulose. The cross-linking degree of the chitosan oligosaccharide cross-linked polymer can be controlled by adjusting the ratio of the raw materials and the drying conditions. The invention also provides food-grade superabsorbent particles. The food-grade superabsorbent particles contain the chitosan oligosaccharide cross-linked polymer. The food-grade superabsorbent particles can be used as a food additive for providing strong satiety and physiological activity of chitosan oligosaccharide, can be used as a main material or an auxiliary material of products such as solid beverages, candies, pet foods, tablets, capsules, electuary and the like, and can be widely applied to the fields of foods, medicines and medical instruments.

Description

Technical Field

[0001] The present invention relates to the field of supramolecular polymers, and particularly to a chitosan cross-linked polymer based on cross-linked carboxymethyl cellulose sodium with chitosan oligosaccharide, a preparation method thereof, and applications in the fields of functional foods, pharmaceuticals, and medical devices. Background Art

[0002] In recent years, hydrogels, as a new type of product that can provide a sense of fullness and assist in weight loss, have gradually become commercialized and entered the consumer market. Cation-anion cross-linking is one of the important means to form such hydrogels. Among them, chitosan and chitosan oligosaccharide are common cationic polymers. For example, CN104367589A discloses an edible fiber supplement and its application in suppressing appetite. In this technical solution, the edible fiber supplement combination includes at least one cationic polymer such as chitosan oligosaccharide and at least one anionic polymer such as sodium alginate. Both are dissolved or dispersed in an aqueous solution. When the pH of this aqueous solution decreases, such as in the acidic environment of the stomach after ingestion or by adding some acidifying agent to this aqueous solution, this aqueous solution will turn into a gel. However, the digestion mechanism of the gel formed in this technical solution is unclear, the size of the gel formed in the stomach is uncontrollable, and although it can be dissolved in a slightly alkaline environment, the pH of the small intestine is generally considered to be about 6.8, and the gel formed cannot be fully dissociated, posing risks such as intestinal obstruction. Another example is that CN 113519851 A, CN 115154407 B, etc. disclose that chitosan-based hydrogels can maintain integrity in the stomach and dissociate in the intestine. However, according to the national standard GB2760-2024 "National Food Safety Standard - Standard for the Use of Food Additives", chitosan can only be used as a thickening agent and coating agent in Western-style ham (smoked, smoked, steamed ham) and meat sausage foods as a food additive. Therefore, the application of such products as foods or food additives is very limited.

[0003] In addition, the inventors found in practice that when chitosan oligosaccharide is blended with an anionic polymer in water, especially when the system viscosity is high, chitosan oligosaccharide and the anionic polymer are extremely likely to form dense lumps locally after contact, and the formed lumps are difficult to effectively disperse in a short time. Summary of the Invention

[0004] In view of the above background, in order to improve the safety, composite functionality of hydrogel products containing cationic polymers, expand their application scope, and improve the mixing efficiency during preparation, the present invention provides a chitosan cross-linked polymer using a monovalent metal salt of an organic acid as a cross-linking regulator and co-solvent, a preparation method thereof, and its applications in the fields of food, medicine, and medical devices.

[0005] The first aspect of the present invention provides a chitosan cross-linked polymer, which at least contains chitosan, sodium carboxymethyl cellulose and a monovalent metal salt of organic acid. The chitosan cross-linked polymer is at least cross-linked by the physical interaction between the amino group in chitosan and the carboxyl group in sodium carboxymethyl cellulose.

[0006] In a preferred embodiment of the present invention, the degree of substitution of the sodium carboxymethyl cellulose is not less than 0.6, and the viscosity of the 1% aqueous solution prepared from the sodium carboxymethyl cellulose is 200-4000 mPa·s at 25°C.

[0007] Among them, the content of the chitosan is preferably 1%-10% of the mass of the sodium carboxymethyl cellulose.

[0008] In a preferred embodiment of the present invention, the organic acid in the monovalent metal salt of organic acid is selected from one or more of citric acid, malic acid, gluconic acid, lactic acid, and is preferably citric acid. The monovalent metal in the monovalent metal salt of organic acid is selected from one or two of sodium and potassium, and is preferably potassium or contains both sodium and potassium.

[0009] Among them, the mass ratio of the chitosan to the monovalent metal salt of organic acid is preferably 1:0.1 to 1:2.

[0010] The present invention also provides a preparation method of the chitosan cross-linked polymer. The preparation method of the chitosan cross-linked polymer at least includes the following steps:

[0011] S1. Mix each raw material with water in the required proportion until it is completely dispersed and uniform to obtain a water mixture;

[0012] S2. Transfer and spread the water mixture into an anti-sticking container, and dry the water mixture at a temperature of 50-105°C to obtain a solid complex.

[0013] In a preferred embodiment of the present invention, after adding the monovalent metal salt of organic acid, the liquid absorption multiple of the obtained chitosan cross-linked polymer after swelling in the 1 / 10 diluted simulated gastric juice with pH = 2.5 for 1 hour is increased by at least 5%.

[0014] In a preferred embodiment of the present invention, after adding the monovalent metal salt of organic acid, the liquid absorption multiple of the obtained chitosan cross-linked polymer after swelling in the 1 / 10 diluted simulated gastric juice with pH = 2.5 for 1 hour is decreased by at least 5%.

[0015] In a preferred embodiment of the present invention, after adding the monovalent metal salt of organic acid, the change in the liquid absorption multiple of the obtained chitosan cross-linked polymer after swelling in the 1 / 10 diluted simulated gastric juice with pH = 2.5 for 1 hour is less than ±5%.

[0016] In a preferred embodiment of the present invention, the chitosan crosslinked polymer does not contain a crosslinking agent that forms a chemical crosslink or a strong physical crosslink with any raw material.

[0017] The second aspect of the present invention provides a food-grade superabsorbent particle, and the food superabsorbent particle contains at least one chitosan crosslinked polymer. The chitosan crosslinked polymer contains at least chitosan, sodium carboxymethylcellulose, and a monovalent metal salt of an organic acid. The chitosan crosslinked polymer is crosslinked at least by the physical interaction between the amino group in chitosan and the carboxyl group in sodium carboxymethylcellulose.

[0018] In a preferred embodiment of the present invention, the degree of substitution of the sodium carboxymethylcellulose is not less than 0.6. The viscosity of the 1% aqueous solution prepared from the sodium carboxymethylcellulose is 200 - 4000 mPa·s at 25°C.

[0019] Among them, the content of the chitosan is 1% - 10% of the mass of the sodium carboxymethylcellulose.

[0020] In a preferred embodiment of the present invention, the organic acid in the monovalent metal salt of the organic acid is selected from one or more of citric acid, malic acid, gluconic acid, and lactic acid, and preferably citric acid.

[0021] In a preferred embodiment of the present invention, the monovalent metal in the monovalent metal salt of the organic acid is selected from one or both of sodium and potassium, and preferably potassium or contains both sodium and potassium.

[0022] Among them, the mass ratio of the chitosan to the monovalent metal salt of the organic acid is 1:0.1 to 1:2.

[0023] The food-grade superabsorbent particle contains or does not contain other food additives, and does not contain a crosslinking agent that forms a chemical crosslink or a strong physical crosslink with any raw material.

[0024] The food-grade superabsorbent particle is obtained by further pulverizing and sieving the chitosan crosslinked polymer existing in the form of a solid complex as described above.

[0025] Among them, the particle size of the particle is preferably 0.1 - 1 mm, and more preferably 0.4 - 1 mm.

[0026] The liquid absorption multiple of the food-grade superabsorbent particle after swelling in 1 / 10 simulated gastric juice for 1 hour is not less than 60 times. The change in the liquid absorption multiple of the food-grade superabsorbent particle after swelling in 1 / 10 simulated gastric juice at pH = 2.5 for 3 hours compared with the liquid absorption multiple after swelling for 1 hour is preferably not more than ±25%. The food-grade superabsorbent particle is completely dissociated or the swelling residue no longer maintains a granular state after swelling in simulated intestinal fluid for 2 hours.

[0027] The third aspect of the present invention provides a product for providing high-efficiency satiety, and the product for providing high-efficiency satiety contains a food-grade superabsorbent particle as described above in an amount of 0.1-99.9% by mass. The product for providing high-efficiency satiety is a food, a drug or a medical device. The form of the food is a solid beverage, a candy or a pet food; the form of the drug or the medical device is a tablet, a capsule or a granule.

[0028] In one embodiment of the present invention, the product for providing high-efficiency satiety contains no more than 3 g of food-grade superabsorbent particles per single-use portion, preferably 2-3 g.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] 1. The chitosan cross-linked polymer and the corresponding food-grade superabsorbent particles provided by the present invention swell at a high multiple in the stomach but dissociate in the intestine. The product containing the food-grade superabsorbent particles of the present invention can not only provide a strong sense of satiety during the gastric digestion stage, but also naturally dissociate within two hours after entering the intestine, greatly reducing the probability of side effects such as intestinal obstruction.

[0031] 2. The chitosan involved in the food-grade superabsorbent particles of the present invention not only plays a structural role as a cross-linking agent in the polymer structure, but also has the effects of weight loss and lipid reduction and other physiological activities. Therefore, the food-grade superabsorbent particles of the present invention have both a structural role and corresponding biochemical effects while keeping the raw materials and structure simple and without adding additional active ingredients.

[0032] 3. After adding a monovalent metal salt of an organic acid, it can play a regulating role in the cross-linking of chitosan, introducing a new means for product performance regulation. On the one hand, under specific ratios and process conditions, adding a monovalent metal salt of an organic acid can greatly increase the liquid absorption multiple of the obtained particles, which provides a solution for increasing the chitosan content to fully exert its physiological activity while not reducing the liquid absorption multiple and satiety of the particles. On the other hand, under specific ratios and process conditions, adding a small amount of a monovalent metal salt of an organic acid can greatly increase the cross-linking efficiency of chitosan, manifested as a decrease in the liquid absorption multiple. In addition, under specific ratios and process conditions, adding a monovalent metal salt of an organic acid can accelerate the dissolution of chitosan in a high-viscosity system, shorten the process time and improve the production efficiency, regardless of whether it changes the swelling performance of the obtained polymer and particles.

[0033] 4. The sodium carboxymethyl cellulose used for preparing the food-grade superabsorbent particles is listed in the "List of Food Additives That Can Be Used in Appropriate Quantities as Needed in Various Foods" in the "National Food Safety Standard - Standards for the Use of Food Additives" (GB 2760-2014). The chitosan oligosaccharide used for preparing the food-grade superabsorbent particles is a new food raw material. Both are ingredients that are safe and harmless to the human body and can be used to prepare various types of ordinary foods.

[0034] Reference will be made to the following description of embodiments, examples and the appended claims, and these and other features and advantages of the present invention will become apparent. Detailed Embodiments

[0035] Chitosan oligosaccharide cross-linked polymer

[0036] The present invention provides a chitosan oligosaccharide cross-linked polymer, which at least contains chitosan oligosaccharide, sodium carboxymethyl cellulose and monovalent metal salts of organic acids, and is at least cross-linked by physical interaction between the amino groups in the chitosan oligosaccharide and the carboxyl groups in the sodium carboxymethyl cellulose.

[0037] In a preferred embodiment of the present invention, the degree of substitution of the sodium carboxymethyl cellulose is not less than 0.6, and the viscosity of the 1% aqueous solution prepared from the sodium carboxymethyl cellulose at 25°C is 200-4000 mPa·s.

[0038] Among them, the content of the chitosan oligosaccharide is preferably 1%-10% of the mass of the sodium carboxymethyl cellulose.

[0039] In a preferred embodiment of the present invention, the organic acid in the monovalent metal salt of the organic acid is selected from one or more of citric acid, malic acid, gluconic acid, and lactic acid, and is preferably citric acid.

[0040] In a preferred embodiment of the present invention, the monovalent metal in the monovalent metal salt of the organic acid is selected from one or two of sodium and potassium, and is preferably potassium or contains both sodium and potassium.

[0041] Among them, the mass ratio of the chitosan oligosaccharide to the monovalent metal salt of the organic acid is preferably 1:0.1 to 1:2. In a preferred embodiment of the present invention, the mass ratio of the chitosan oligosaccharide to the monovalent metal salt of the organic acid is 1:0.5 to 1:2. In a preferred embodiment of the present invention, the mass ratio of the chitosan oligosaccharide to the monovalent metal salt of the organic acid is 1:0.1 to 1:0.25.

[0042] The present invention also provides a method for preparing the chitosan oligosaccharide cross-linked polymer. The method for preparing the chitosan oligosaccharide cross-linked polymer at least includes the following steps:

[0043] S1. Mix each raw material with water in the required proportions until completely dispersed and uniform to obtain a water mixture;

[0044] S2. Transfer and spread the water mixture evenly in a non-stick container, and dry the water mixture at a temperature of 50 - 105 °C to obtain a solid complex.

[0045] In a preferred embodiment of the present invention, step S2 in the preparation method of the chitosan oligosaccharide cross-linked polymer further comprises at least the following steps:

[0046] S2.1. Transfer and spread the water mixture evenly in a non-stick container, and dry the water mixture at a temperature of 50 - 105 °C to obtain a first-dried solid complex;

[0047] S2.2. Second-dry the first-dried solid complex obtained in S2.1 at a temperature of 80 - 105 °C for 2 - 8 hours to obtain a second-dried solid complex.

[0048] Among them, the non-stick container described in step S2.1 is preferably a container made of polytetrafluoroethylene, polypropylene, or silicone rubber, or a container made of other materials lined with a non-stick film. Among them, the non-stick film is preferably non-stick cloth, polytetrafluoroethylene film, polypropylene film, or silicone rubber film.

[0049] Among them, in the non-stick container, the water mixture is preferably spread into a coating no more than 3 cm thick, and more preferably spread into a coating no more than 2 cm thick.

[0050] Among them, the drying method is not particularly limited, and preferably is air-blowing drying or vacuum drying.

[0051] Among them, the drying temperature described in step S2.1 is preferably not higher than 80 °C. When the drying temperature is greater than 85 °C, for a water mixture with a higher concentration and a thicker coating, a dry and dense skin is likely to form on the surface of the water mixture first, preventing the evaporation of internal moisture, and instead requiring a longer drying time. Using a higher drying temperature not only does not improve the drying efficiency, but also wastes energy. Therefore, a drying temperature not higher than 80 °C is more preferred. Considering that the higher the drying temperature, the shorter the required drying time, the most preferred is 80 °C.

[0052] Among them, the higher the second-drying temperature in step S2.2, the higher the cross-linking efficiency, and the shorter the cross-linking time required to obtain a chitosan oligosaccharide cross-linked polymer with a similar degree of cross-linking. Therefore, it is preferably 95 - 105 °C.

[0053] Among them, the obtained solid complex, first-dried solid complex, and second-dried solid complex are all the chitosan oligosaccharide cross-linked polymer described in the present invention. The difference is that due to possible differences in drying conditions, the degrees of cross-linking of the corresponding chitosan oligosaccharide cross-linked polymers obtained are also different.

[0054] In a preferred embodiment of the present invention, before the step S1 in the preparation method of the chitosan cross-linked polymer, the following premixing step S0 is further included:

[0055] S0. Mix sodium carboxymethylcellulose with drinking water to obtain a micelle; wherein, the mass of sodium carboxymethylcellulose accounts for 10-25% of the total mass of the micelle.

[0056] In a preferred embodiment of the present invention, in step S0, the mass of sodium carboxymethylcellulose preferably accounts for 10-20% of the total mass, more preferably 13-18% of the total mass, and most preferably 15-17% of the total mass. When the water content of the micelle is higher, the raw material powder of sodium carboxymethylcellulose in the micelle is more fully wetted by water, which is beneficial to further shorten the mixing time of step S1.

[0057] The crosslinking degree of the chitosan cross-linked polymer of the present invention is affected by various factors, including but not limited to the dosage of chitosan as a crosslinking agent, drying temperature, drying duration, mixing concentration, dosage of organic acid monovalent metal salt, etc. Generally speaking, the larger the dosage of chitosan, the higher the crosslinking degree, and the lower the liquid absorption multiple; the higher the drying temperature, the higher the crosslinking degree, and the lower the liquid absorption multiple; the longer the drying duration, the higher the crosslinking degree, and the lower the liquid absorption multiple. Too high mixing concentration will affect the dispersion of materials, and then affect the physical crosslinking of anions and cations between chitosan and sodium carboxymethylcellulose. The influence of organic acid monovalent metal salt on the crosslinking degree is more complicated. According to experimental phenomena, on the one hand, adding organic acid monovalent metal salt can weaken the aggregation between chitosan and chitosan, which is beneficial to the increase of crosslinking points, thus reducing the liquid absorption multiple. On the other hand, adding organic acid monovalent metal salt can weaken the anion-cation interaction between chitosan and sodium carboxymethylcellulose, which helps to reduce the crosslinking degree of chitosan cross-linked polymer and increase the liquid absorption multiple. When it is excessive, it even destroys the crosslinking effect. And when these two effects reach a balance and offset each other, the influence on the liquid absorption multiple is not significant.

[0058] It should be noted that in the present invention, the drying temperature and drying duration not only affect the crosslinking degree of the chitosan crosslinked polysaccharide polymer, but also the increased drying temperature and extended drying duration can also improve the crosslinking degree of sodium carboxymethylcellulose without chitosan. Under the action of the drying temperature, the specific chemical or physical structure of the crosslinking points of thermally induced crosslinking of sodium carboxymethylcellulose or its complex with chitosan is not yet clear, and there are various possibilities. One possibility is that sodium carboxymethylcellulose is thermally induced to form crystals, and another possibility is that heating further removes the bound water in the complex, resulting in enhanced cation-anion interactions between sodium carboxymethylcellulose and chitosan. Although the mechanism of thermally induced crosslinking is not yet clear, it has repeatability in practice, and those skilled in the art can adjust parameters such as the dosage of chitosan, drying temperature, drying duration, mixing concentration, and dosage of the monovalent metal salt of organic acid according to actual needs, so as to obtain a chitosan crosslinked polysaccharide polymer with the desired chitosan content and crosslinking degree.

[0059] In a preferred embodiment of the present invention, after adding the monovalent metal salt of the organic acid, the liquid absorption multiple of the obtained chitosan crosslinked polymer after swelling in 1 / 10 diluted simulated gastric juice with pH = 2.5 for 1 hour is increased by at least 5%, preferably at least 10%, more preferably at least 20%, more preferably at least 30%, more preferably at least 40%, more preferably at least 50%.

[0060] In a preferred embodiment of the present invention, after adding the monovalent metal salt of the organic acid, the liquid absorption multiple of the obtained chitosan crosslinked polymer after swelling in 1 / 10 diluted simulated gastric juice with pH = 2.5 for 1 hour is decreased by at least 5%, preferably at least 10%, more preferably at least 20%, more preferably at least 30%, more preferably at least 40%, more preferably at least 50%.

[0061] In a preferred embodiment of the present invention, after adding the monovalent metal salt of the organic acid, the change in the liquid absorption multiple of the obtained chitosan crosslinked polymer after swelling in 1 / 10 diluted simulated gastric juice with pH = 2.5 for 1 hour is less than ±5%.

[0062] Among them, the 1 / 10 diluted simulated gastric juice with pH = 2.5 is obtained by diluting the artificial gastric juice (pH = 1.5) in the Chinese Pharmacopoeia 2020 edition by 10 times and then adjusting the pH to 2.5.

[0063] In a preferred embodiment of the present invention, the chitosan cross-linked polymer does not contain a cross-linking agent that forms a chemical cross-link or a strong physical cross-link with any raw material. By way of example, the cross-linking agent that forms a chemical cross-link with the raw material includes but is not limited to polycarboxylic acids. Specifically, by way of example, the cross-linking agent that forms a chemical cross-link with the raw material includes but is not limited to citric acid, malic acid, tartaric acid, fumaric acid, succinic acid, etc. By way of example, the cross-linking agent that forms a strong physical cross-link with the raw material includes but is not limited to metal ions of trivalent or higher. Specifically, by way of example, the cross-linking agent that forms a strong physical cross-link with the raw material includes but is not limited to ferric ions, aluminum ions, etc.

[0064] Food-grade superabsorbent particles

[0065] The present invention also provides a food-grade superabsorbent particle, and the food superabsorbent particle contains at least one chitosan cross-linked polymer. The chitosan cross-linked polymer contains at least chitosan, sodium carboxymethyl cellulose, and a monovalent metal salt of an organic acid. The chitosan cross-linked polymer is cross-linked at least by the physical interaction between the amino group in chitosan and the carboxyl group in sodium carboxymethyl cellulose.

[0066] In a preferred embodiment of the present invention, the degree of substitution of the sodium carboxymethyl cellulose is not less than 0.6, preferably not less than 0.9. The viscosity of an aqueous solution with a mass concentration of 1% prepared from the sodium carboxymethyl cellulose is 200 - 4000 mPa·s at 25°C, preferably 1000 - 4000 mPa·s, and more preferably 3000 - 4000 mPa·s.

[0067] Among them, the content of the chitosan is 1% - 10% of the mass of the sodium carboxymethyl cellulose.

[0068] In a preferred embodiment of the present invention, the organic acid in the monovalent metal salt of the organic acid is selected from one or more of citric acid, malic acid, gluconic acid, and lactic acid, preferably citric acid.

[0069] In a preferred embodiment of the present invention, the monovalent metal in the monovalent metal salt of the organic acid is selected from one or two of sodium and potassium, preferably potassium or containing both sodium and potassium.

[0070] Among them, the mass ratio of the chitosan to the monovalent metal salt of the organic acid is 1:0.1 to 1:2. In a preferred embodiment of the present invention, the mass ratio of the chitosan to the monovalent metal salt of the organic acid is 1:0.5 to 1:2. In a preferred embodiment of the present invention, the mass ratio of the chitosan to the monovalent metal salt of the organic acid is 1:0.1 to 1:0.25.

[0071] The food-grade superabsorbent particles contain or do not contain other food additives. By way of example, the other food additives include, but are not limited to, sugar alcohols, fructooligosaccharides, L-carnitine, probiotics, animal extracts, plant extracts, mushroom extracts, etc.

[0072] In the present invention, the food-grade superabsorbent particles do not contain a crosslinking agent that forms a chemical crosslink or a strong physical crosslink with any raw material. By way of example, the crosslinking agent that forms a chemical crosslink with the raw material includes, but is not limited to, polycarboxylic acids. Specifically, by way of example, the crosslinking agent that forms a chemical crosslink with the raw material includes, but is not limited to, citric acid, malic acid, tartaric acid, fumaric acid, succinic acid, etc. By way of example, the crosslinking agent that forms a strong physical crosslink with the raw material includes, but is not limited to, metal ions of trivalent or higher valence. Specifically, by way of example, the crosslinking agent that forms a strong physical crosslink with the raw material includes, but is not limited to, ferric ions, aluminum ions, etc. If the crosslinking agent that can form a chemical crosslink or a strong physical crosslink with the raw material is used, strong crosslinks that are difficult to dissociate in the intestine may be formed during the preparation process.

[0073] The food-grade superabsorbent particles are obtained by further pulverizing and screening the chitosan crosslinked polymer in the form of a solid complex described above. Specifically, the preparation method of the food-grade superabsorbent particles at least includes the following steps:

[0074] S1. Mix each raw material with water in the required proportion until it is completely dispersed and uniform to obtain a water mixture.

[0075] S2. Transfer the water mixture and spread it flat in a heat-resistant and non-sticky container, and dry the water mixture at a temperature of 50-105 °C to obtain a solid complex.

[0076] S3. Pulverize and screen the obtained solid complex to obtain the food-grade superabsorbent particles.

[0077] The water therein is drinking pure water or drinking deionized water.

[0078] In a preferred embodiment of the present invention, the preparation method of the food-grade superabsorbent particles further includes the following premixing step S0 before the step S1:

[0079] S0. Mix sodium carboxymethylcellulose with drinking water to obtain a micelle; wherein, the mass of sodium carboxymethylcellulose accounts for 10-25% of the total mass of the micelle.

[0080] Among them, in step S0, the mass of sodium carboxymethylcellulose preferably accounts for 10-20% of the total mass, more preferably 13-18% of the total mass, and most preferably 15-17% of the total mass. When the water content of the micelle is higher, the raw material powder of sodium carboxymethylcellulose in the micelle is more fully wetted by water, which is beneficial to further shorten the mixing time of step S1.

[0081] In a preferred embodiment of the present invention, step S2 in the preparation method of the food-grade superabsorbent particles further includes at least the following steps:

[0082] S2.1. Transfer the water mixture to an anti-sticking container, and dry the water mixture at a temperature of 50-80°C to obtain a primary dried solid complex;

[0083] S2.2. Secondarily dry the primary dried solid complex obtained in S2.1 at a temperature of 80-105°C for 2-8 hours to obtain a secondary dried solid complex.

[0084] Among them, the anti-sticking container described in step S2.1 is preferably a container made of polytetrafluoroethylene, polypropylene, or silicone rubber for food contact, or a container made of other materials lined with an anti-sticking film. Among them, the anti-sticking film is preferably an anti-sticking cloth for food contact, a polytetrafluoroethylene film, a polypropylene film, or a silicone rubber film.

[0085] Among them, in the anti-sticking container, the water mixture is preferably spread into a coating with a thickness of no more than 3 cm, and more preferably spread into a coating with a thickness of no more than 2 cm.

[0086] Among them, the drying method is not particularly limited, and preferably is air drying or vacuum drying.

[0087] Among them, the drying temperature described in step S2.1 is preferably not lower than 70°C. On the one hand, when the drying temperature is too low, the drying time will be greatly prolonged and the production efficiency will also be greatly reduced. On the other hand, a relatively mild drying temperature is instead conducive to the reproduction of harmful microorganisms in the water mixture. Considering that the lethal temperature of general bacteria is about 68°C, therefore, the drying temperature not lower than 70°C is more preferable. Among them, the drying temperature is further preferably not higher than 80°C. When the drying temperature is greater than 85°C, for a water mixture with a higher concentration and a thicker coating, a dry and dense skin is easily formed on the surface of the water mixture first, which prevents the evaporation of internal moisture, and instead requires a longer drying time. Using a higher drying temperature not only does not improve the drying efficiency, but also wastes energy. Therefore, the drying temperature not higher than 80°C is also more preferable. In summary, the drying temperature described in step S2.1 is further preferably 70-80°C, and most preferably 80°C.

[0088] Among them, the higher the secondary drying temperature in step S2.2, the higher the crosslinking efficiency, and the shorter the crosslinking time required to obtain food-grade superabsorbent particles with a similar degree of crosslinking. Therefore, the secondary drying temperature is preferably 95-105°C.

[0089] Among them, step S2.2 can be carried out before step S3 or after step S3. Since the pulverized solid complex is more likely to be packed at a higher density and the volume requirement for the secondary drying equipment is also reduced, it is preferred that step S2.2 be carried out after step S3.

[0090] Among them, the particle size of the particles is preferably 0.1-1 mm, more preferably 0.4-1 mm. When the powder with a particle size less than 0.1 mm encounters water, it quickly agglomerates into large gels and is difficult to disperse. When the particle size is 0.1-0.4 mm, by adding a small amount of dispersant and mixing with water, the particle feeling can be maintained. Therefore, the particle size of the particles is preferably 0.1-1 mm. And when the particle size is 0.4-1 mm, even without adding a dispersant, the particle feeling can still be maintained when mixed with water. Therefore, the particle size of the particles is more preferably 0.4-1 mm.

[0091] The liquid absorption multiple of the food-grade superabsorbent particles after swelling in 1 / 10 simulated gastric juice for 1 hour is not less than 60 times, preferably not less than 70 times, more preferably not less than 80 times, still more preferably not less than 90 times, and even more preferably not less than 100 times. The change in the liquid absorption multiple of the food-grade superabsorbent particles after swelling in 1 / 10 simulated gastric juice with pH = 2.5 for 3 hours compared with that after swelling for 1 hour is preferably no more than ±25%, more preferably no more than ±20%, more preferably no more than ±15%, more preferably no more than ±10%, and most preferably no more than ±5%. By its stable liquid absorption performance, it occupies a certain volume in the stomach and provides a sense of fullness for a longer time after eating.

[0092] The food-grade superabsorbent particles are completely dissociated or the swelling residue no longer maintains a granular state after swelling in simulated intestinal fluid for 2 hours.

[0093] Among them, the 1 / 10 diluted simulated gastric juice with pH = 2.5 is obtained by diluting the artificial gastric juice (pH = 1.5) in the Chinese Pharmacopoeia 2020 Edition by 10 times and then adjusting the pH to 2.5.

[0094] Among them, the simulated intestinal fluid is the artificial intestinal fluid in the Chinese Pharmacopoeia 2020 Edition, and the pH value is 6.8.

[0095] Products providing high-efficiency satiety

[0096] The present invention also provides a product for providing high-efficiency satiety, and the product contains the aforementioned food-grade superabsorbent particles in an amount of 0.1-99.9% by mass.

[0097] In a preferred embodiment of the present invention, the product is a food, a drug or a medical device. Among them, the form of the food is a solid beverage, a candy, a pet food; the form of the drug or the medical device is a tablet, a capsule, a granule.

[0098] An embodiment of the present invention provides a solid beverage. By way of example, the solid beverage at least comprises the following components:

[0099] Food-grade superabsorbent particles, 100 parts by mass;

[0100] Citric acid, 0.01-5 parts by mass;

[0101] Sweetener, 0.01-5 parts by mass;

[0102] Natural fruit powder, 10-100 parts by mass.

[0103] The solid beverage may further comprise, but is not limited to, other food raw materials or food additives such as hydrolyzed collagen, white kidney bean extract, sugar alcohol, fructooligosaccharide, L-carnitine, probiotics, other animal extracts, other plant extracts, mushroom extracts, etc.

[0104] Mix the above components according to the formula ratio, bag them, and then a solid beverage for providing high-efficiency satiety according to the present invention is obtained. 20-40 minutes before lunch or dinner, pour the solid beverage into 200 mL of room-temperature water, quickly stir until the particles are basically dispersed, drink it within three minutes, and then drink 200 mL of water; have a normal or reduced meal 30 minutes later, which can effectively delay the occurrence of hunger.

[0105] An embodiment of the present invention provides a compressed candy. By way of example, the compressed candy at least comprises the following components:

[0106] Food-grade superabsorbent particles, 100 parts by mass;

[0107] Sugar alcohol, 20-60 parts by mass;

[0108] Magnesium stearate, 1-2 parts by mass;

[0109] Citric acid, 0.1-5 parts by mass;

[0110] Other sweeteners, 0.1-5 parts by mass.

[0111] Fully mix the particles with the excipients and then use a tableting machine to tablet them, and seal the package, and then a candy for providing high-efficiency satiety according to the present invention is obtained.

[0112] Take the tablet candy with 400 mL of water 20 - 40 minutes before lunch or dinner; have a normal or reduced meal 30 minutes later, which can effectively delay the onset of hunger.

[0113] An embodiment of the present invention provides a gummy candy. By way of example, the gummy candy contains at least the following components:

[0114] Food-grade superabsorbent particles, 100 parts by mass;

[0115] Gelatin, 10 - 30 parts by mass;

[0116] Water, 50 - 200 parts by mass;

[0117] Sugar alcohol, 100 - 500 parts by mass;

[0118] Acidulant, 3 - 8 parts by mass;

[0119] Concentrated fruit juice, 50 - 150 parts by mass.

[0120] Mix the raw materials other than the food-grade superabsorbent particles evenly at 90 °C, then fully mix the particles with the mixture and pour it into a mold to cool and form. After demolding, apply an anti-sticking agent and package it tightly to obtain the gummy candy provided by the present invention with high satiety.

[0121] Eat the gummy candy 20 - 40 minutes before lunch or dinner and drink 300 - 500 mL of water; have a normal or reduced meal 30 minutes later, which can effectively delay the onset of hunger.

[0122] An embodiment of the present invention provides a capsule. By way of example, the capsule contains at least the following components:

[0123] Food-grade superabsorbent particles, 100 parts by mass;

[0124] Disintegrant, 5 - 150 parts by mass.

[0125] Take the capsule with 400 mL of water 20 - 40 minutes before lunch or dinner; have a normal or reduced meal 30 minutes later, which can effectively delay the onset of hunger.

[0126] The above examples of the components of the solid beverage, tablet candy, gummy candy, and capsule are only for further detailed description of the present invention and do not limit the protection scope of the present invention.

[0127] In an embodiment of the present invention, each single-use portion of the product providing high satiety contains no more than 3 g of food-grade superabsorbent particles, preferably 0.5 - 3 g, more preferably 1 - 3 g, still more preferably 1.5 - 3 g, and most preferably 2 - 3 g.

[0128] Liquid Absorption Multiple Measurement and Calculation Method

[0129] In the present invention, the measurement and calculation of the liquid absorption multiple in different simulated liquids are carried out according to the following method:

[0130] - Accurately weigh 0.0200 ± 0.0005 g of particles with a particle size of 0.4 - 1 mm, and record the accurate value as M0;

[0131] - Put the weighed particles into a 50 mL beaker that has been preheated in a 37°C water bath and contains 20 mL of simulated liquid (i.e., the mass ratio of particles to simulated liquid is 1:1000), and start timing;

[0132] - Use a 60 mL G1 sintered glass funnel to vacuum filter 20 mL of deionized water, carefully dry the residual liquid at the mouth of the funnel (the lower slender tube part) with filter paper, and accurately weigh the mass of the sintered glass funnel to 0.1 mg, and record the accurate value as M1;

[0133] - After continuously magnetically dispersing and swelling in a 37°C water bath for a specific period of time, vacuum filter the simulated liquid through the above-mentioned 60 mL G1 sintered glass funnel, carefully dry the residual liquid at the mouth of the funnel with filter paper, and accurately weigh the mass of the sintered glass funnel containing the filtration residue to 0.1 mg, and record the accurate value as M2;

[0134] - Calculate the liquid absorption multiple of the particles according to the following formula: Liquid absorption multiple = (M2 - M1) / M0 - 1.

[0135] Raw material viscosity measurement method

[0136] Adopt the viscosity data provided by the raw material supplier, and use a digital rotational viscometer to measure to confirm whether the measured value is within its claimed range.

[0137] Among them, the measurement of the viscosity of sodium carboxymethylcellulose is carried out according to A.4 in the national standard "GB1886.232 - 2016 National Food Safety Standard Food Additive Sodium Carboxymethylcellulose".

[0138] The present invention will be further described below in conjunction with some specific embodiments. The specific embodiments are for further detailed description of the present invention and do not limit the protection scope of the present invention. Unless otherwise specified, the raw materials used in the following examples are all commercially available food-grade raw materials that meet the corresponding national standards.

[0139] Regulating effect of monovalent metal salts of organic acids on crosslinking degree

[0140] (1) Organic Acid vs Inorganic Acid

[0141] Example 1Disperse 20 parts by mass of sodium carboxymethylcellulose (viscosity 200 - 500 mPa·s, type 9), 1 part by mass of chitosan oligosaccharide, and 1 part by mass of sodium citrate in 980 parts by mass of deionized water until uniformly transparent; transfer the mixed solution to a PP plastic container for food contact and dry it in a blast dryer at 80 °C for 16 hours; crush and sieve to obtain component particles with a size of 0.4 - 1 mm, and then dry them at 105 °C for 2 h for subsequent swelling performance testing.

[0142] The preparation method of Reference Example 1 is the same as that of Example 1, except that sodium citrate is not added.

[0143] The preparation method of Comparative Example 1 is the same as that of Example 1, except that sodium chloride is used instead of sodium citrate.

[0144] Table 1 lists the liquid absorption multiples of the particles obtained in Example 1, Reference Example 1, and Comparative Example 1 in 1 / 10 diluted simulated gastric juice (pH = 2.5):

[0145] Table 1

[0146] Sample Monovalent metal salt pH = 2.5, 1 h Reference Example 1 None 58.2 Example 1 Sodium citrate 79.3 Comparative Example 1 Sodium chloride 58.0

[0147] According to the above results, adding sodium citrate can significantly increase the liquid absorption multiple of the particles, while adding sodium chloride has no significant effect on the liquid absorption multiple.

[0148] (2) Types of monovalent metal salts of organic acids

[0149] Examples 2 - 6 Disperse 20 parts by mass of sodium carboxymethylcellulose (viscosity 200 - 500 mPa·s, type 9), 0.5 part by mass of chitosan oligosaccharide, and 0.5 part by mass of monovalent metal salt in 980 parts by mass of deionized water until uniformly transparent; transfer the mixed solution to a PP plastic container for food contact and dry it in a blast dryer at 80 °C for 16 hours; crush and sieve to obtain component particles with a size of 0.4 - 1 mm, and then dry them at 105 °C for 2 h for subsequent swelling performance testing.

[0150] The preparation method of Reference Example 2 is the same as that of Examples 2 - 6, except that no monovalent metal salt of organic acid is added.

[0151] Table 2 lists the liquid absorption multiples of the particles obtained in Examples 2 - 6 and Reference Example 2 in 1 / 10 diluted simulated gastric juice (pH = 2.5) and simulated intestinal fluid (pH = 6.8), and the state of the particles after swelling and filtration in simulated intestinal fluid:

[0152] Table 2

[0153] Sample Monovalent metal salt pH = 2.5, 1 h pH = 2.5, 3 h pH = 6.8, 2 h Reference Example 2 None 84.1 75.5 17.2, trace amount of soft amorphous residue Example 2 Sodium citrate 109.7(+30.4％) 89.2 22.9, small amount of soft amorphous residue Example 3 Potassium citrate 112.2(+33.4％) 73.0 19.4, small amount of soft amorphous residue Example 4 Sodium malate 95.5(+13.6％) 90.1 13.2, trace amount of soft amorphous residue Example 5 Sodium lactate 97.8(+16.3％) 91.3 20.8, small amount of soft amorphous residue Example 6 Sodium gluconate 90.4(+7.5％) 79.5 15.7, trace amount of soft amorphous residue

[0154] According to the above results, all monovalent metal salts of various organic acids can increase the liquid absorption multiple of the particles in 1 / 10 simulated gastric juice at pH = 2.5 for 1 h to varying degrees. With the extension of the swelling time, there is a tendency for the liquid absorption multiples to converge. In addition, the addition of monovalent metal salts of various organic acids does not affect the good dissociation performance of the particles in simulated intestinal fluid at pH = 6.8. Among them, potassium citrate and sodium citrate have a more significant effect on improving the liquid absorption multiple of the particles, so they are more preferred. Among them, potassium citrate has a better effect than sodium citrate, so it is the most preferred.

[0155] (3) Influence of dosage of monovalent metal salts of organic acids on crosslinking degree

[0156] Taking potassium citrate and sodium citrate as examples, the effects of the dosages of monovalent metal salts of organic acids on the crosslinked system were investigated.

[0157] Examples 7, Comparative Example 2 Disperse 20 parts by mass of sodium carboxymethylcellulose (viscosity 200 - 500 mPa·s, type 9), 0.5 part by mass of chitosan oligosaccharide, and a certain amount of potassium citrate in 980 parts by mass of deionized water until it is uniformly transparent; dry the mixed solution in a food-contact PP plastic container at 80 °C with forced air for 16 hours; crush and sieve to obtain 0.4 - 1 mm component particles, and then dry them at 105 °C for 2 h for subsequent swelling performance testing.

[0158] Table 3 lists the liquid absorption multiples of the particles obtained in Example 3, Example 7, and Comparative Example 2 in 1 / 10 diluted simulated gastric juice (pH = 2.5) and simulated intestinal fluid (pH = 6.8), as well as the states of the particles after swelling and filtration in simulated intestinal fluid:

[0159] Table 3

[0160]

[0161] The above examples show that when the mass ratio of potassium citrate to chitosan oligosaccharide is in the range of 0.1 - 2 times, chitosan oligosaccharide crosslinked polymers can be formed, and they can all increase the liquid absorption multiple of the particles in 1 / 10 simulated gastric juice at pH = 2.5 for 1 h to varying degrees. The obtained crosslinked polymers are significantly dissociated after swelling in simulated intestinal fluid at pH = 6.8 for 2 h, and only a trace amount or a small amount of soft amorphous residue remains in the funnel after filtration. In contrast, when the dosage of potassium citrate is too high, when it is 5 times the mass of chitosan oligosaccharide, the obtained crosslinked polymer has a dissociation tendency.

[0162] Example 8: 20 parts by mass of sodium carboxymethyl cellulose (viscosity 200 - 500 mPa·s, type 9) and a certain amount of chitosan oligosaccharide and sodium citrate with the same mass as the chitosan oligosaccharide were dispersed in 980 parts by mass of deionized water until uniformly transparent; the mixed solution was dried in a food-contact PP plastic container at 80 °C with forced air for 16 hours; it was pulverized and the 0.4 - 1 mm component particles were sieved, and then dried at 105 °C for another 2 h for subsequent swelling property tests.

[0163] Reference Example 3 The preparation method was the same as that of Example 8, except that sodium citrate was not added.

[0164] Table 4 lists the liquid absorption multiples of the particles obtained in Reference Examples 1 - 3 and Examples 1, 2, and 8 in 1 / 10 diluted simulated gastric juice (pH = 2.5):

[0165] Table 4

[0166] Chitosan oligosaccharide content Reference Example pH = 2.5, 1 h Example pH = 2.5, 1 h 10％ Reference Example 3 - 1 45.4 Example 8 - 1 77.9(+71.6％) 5％ Reference Example 1 58.2 Example 1 79.3(+36.3％) 2.5％ Reference Example 2 84.1 Example 2 109.7(+30.4％) 1％ Reference Example 3 - 2 107.4 Example 8 - 2 112.4(+4.7％)

[0167] The above examples show that when the mass ratio of potassium citrate to chitosan oligosaccharide is 1, and when the amount of chitosan oligosaccharide is in the range of 1% - 10% of the mass of sodium carboxymethyl cellulose, the liquid absorption multiple of the particles in 1 / 10 simulated gastric juice (pH = 2.5) within 1 h can be improved, and with the increase of the chitosan oligosaccharide content, the improvement amplitude is also greater.

[0168] (4) Influence of drying conditions on crosslinking degree

[0169] Example 9 A total of 20 parts by mass of sodium carboxymethyl cellulose (viscosity 3000 - 4000 mPa·s, type 9), 0.5 part by mass of chitosan oligosaccharide, and a certain amount of potassium citrate were dispersed in 980 parts by mass of deionized water until uniformly transparent; the mixed solution was dried in a food-contact PP plastic container at 80 °C with forced air for 16 hours; it was pulverized and the 0.4 - 1 mm component particles were sieved, and then dried at 95 °C with forced air for another 2 h for subsequent swelling property tests.

[0170] The preparation method of Reference Example 4 was the same as that of Example 9, except that potassium citrate was not added.

[0171] Example 10: A total of 20 parts by mass of sodium carboxymethyl cellulose (viscosity 3000 - 4000 mPa·s, type 9), 0.5 part by mass of chitosan oligosaccharide, and a certain amount of potassium citrate were dispersed in 980 parts by mass of deionized water until uniformly transparent; the mixed solution was dried in a food-contact PP plastic container at 80 °C with forced air for 16 hours; it was pulverized and the 0.4 - 1 mm component particles were sieved, and then dried at 105 °C with forced air for another 2 h for subsequent swelling property tests.

[0172] The preparation method of Reference Example 5 was the same as that of Example 10, except that potassium citrate was not added.

[0173] Table 5 lists the liquid absorption multiples of the particles obtained in Examples 9 and 10 and Comparative Examples 3 and 4 in 1 / 10 diluted simulated gastric juice (pH = 2.5):

[0174] Table 5

[0175] Potassium citrate dosage Sample pH = 2.5, 1 h Sample pH = 2.5, 1 h 0 Reference Example 4 97.5 Reference Example 5 80.5 0.1 times Example 9 - 5 102.3(+4.9％) Example 10 - 5 60.9(-24.3％) 0.25 times Example 9 - 4 108.0(+10.8％) Example 10 - 4 66.9(-16.9％) 0.5 times Example 9 - 3 114.4(+17.3) Example 10 - 3 82.5(+2.5％) 1 times Example 9 - 2 133.0(+36.4％) Example 10 - 2 89.7(+11.4％) 2 times Example 9 - 1 140.0(+43.6％) Example 10 - 1 107.8(+33.9％)

[0176] The above examples show that the particles obtained at a higher secondary drying temperature have a lower liquid absorption multiple and a higher crosslinking degree. Unexpectedly, when the secondary crosslinking temperature is 105 °C, the liquid absorption multiple of the particles obtained by adding a small amount of potassium citrate (0.1 - 0.25 times the amount of chitosan oligosaccharide) is lower than that of the particles without adding potassium citrate. It is speculated that this is because the addition of a monovalent metal salt of organic acid can weaken the aggregation between chitosan oligosaccharides, which is beneficial to the increase of crosslinking points, thereby reducing the liquid absorption multiple. At the same time, it also illustrates the complexity of the influence of monovalent metal salts of organic acids on crosslinking, which does not follow a single rule.

[0177] (5) Influence of the viscosity of sodium carboxymethylcellulose

[0178] In Example 11, 20 parts by mass of sodium carboxymethylcellulose (viscosity 200 - 500 mPa·s, type 6), 0.5 parts by mass of chitosan oligosaccharide, and 0.5 parts by mass of potassium citrate were dispersed in 980 parts by mass of deionized water until uniformly transparent; the mixed solution was transferred to a PP plastic container for food contact and dried in a blast dryer at 80 °C for 16 hours; the mixture was pulverized and sieved to obtain particles with a particle size of 0.4 - 1 mm for subsequent swelling property tests.

[0179] Reference Example 6 The preparation method was the same as that of Example 11, except that potassium citrate was not added.

[0180] In Example 12, 20 parts by mass of sodium carboxymethylcellulose (viscosity 1000 - 2000 mPa·s, type 6), 0.5 parts by mass of chitosan oligosaccharide, 0.5 parts by mass of potassium citrate, and different parts by mass of chitosan oligosaccharide were dispersed in 980 parts by mass of deionized water until uniformly transparent; the mixed solution was transferred to a PP plastic container for food contact and dried in a blast dryer at 80 °C for 16 hours; the mixture was pulverized and sieved to obtain particles with a particle size of 0.4 - 1 mm, and then dried at 90 °C for 2 h for subsequent swelling property tests.

[0181] Reference Example 7 The preparation method was the same as that of Example 12, except that potassium citrate was not added.

[0182] Example 13: 20 parts by mass of sodium carboxymethyl cellulose (viscosity 1000 - 2000 mPa·s, type 9), 0.5 part by mass of chitosan oligosaccharide, 0.5 part by mass of potassium citrate and different parts by mass of chitosan oligosaccharide were dispersed in 980 parts by mass of deionized water until uniformly transparent; the mixed solution was transferred to a PP food-contact plastic container and dried in a blast dryer at 80 °C for 16 hours; the mixture was crushed and sieved to obtain component particles with a size of 0.4 - 1 mm, and then dried at 100 °C for 2 h for subsequent swelling performance testing.

[0183] Reference Example 8: The preparation method was the same as that of Example 13, except that potassium citrate was not added.

[0184] Table 6 shows the liquid absorption multiples of the particles obtained in Examples 11 - 13 and Reference Examples 6 - 8 in 1 / 10 diluted simulated gastric juice (pH = 2.5):

[0185] Table 6

[0186] Sample pH = 2.5, 1 h Sample pH = 2.5, 1 h Reference Example 6 74.3 Example 11 101.3(+36.3％) Reference Example 7 66.5 Example 12 90.8(+36.5％) Reference Example 8 94.6 Example 13 118.5(+25.3％)

[0187] The above examples show that when the mass ratio of potassium citrate to chitosan oligosaccharide is 1, by selecting sodium carboxymethyl cellulose with different viscosities and suitable drying conditions, it was observed that the liquid absorption multiple of the cross-linked polymer particles obtained after using potassium citrate increased after 1 hour in 1 / 10 simulated gastric juice at pH = 2.5.

[0188] Promotion effect of monovalent metal salts of organic acids on blending

[0189] Mixing Example 1 Weighed 40 g of sodium carboxymethyl cellulose (viscosity 3000 - 4000 mPa·s, type 9) and 360 g of drinking water into a planetary mixer, and mixed at low speed for 5 minutes, then continued to mix at medium speed for 20 minutes until no white lumps were visually observed. 1 g of chitosan oligosaccharide and 0.5 g of potassium citrate were fully dissolved in 50 g of drinking water. 200 g of drinking water was added to the planetary mixer, and the composite aqueous solution of chitosan oligosaccharide and potassium citrate was quickly poured in. The composite aqueous solution container was rinsed several times with a small amount of water and poured into the planetary mixer, and water was added to make the total mass of the materials reach 800 g. Mixed at low speed for 5 minutes, and a small amount of light yellow filamentous substances were visually observed; then continued to mix at medium speed for 20 minutes until it was visually uniform; continued to mix at medium speed for 20 minutes to ensure uniform mixing of the materials.

[0190] Mixing Example 2 Weigh 40 g of sodium carboxymethylcellulose (viscosity 3000 - 4000 mPa·s, Type 9) and 360 g of drinking water into a planetary mixer, mix at low speed for 5 minutes, then continue to mix at medium speed for 20 minutes. Check visually to ensure there are no white lumps. Dissolve 1 g of chitosan oligosaccharide and 1 g of potassium citrate in 50 g of drinking water. Add 200 g of drinking water to the planetary mixer, quickly pour in the composite aqueous solution of chitosan oligosaccharide and potassium citrate, wash the container of the composite aqueous solution with a small amount of water multiple times, and make up the water to a total material mass of 800 g. Mix at low speed for 5 minutes, check visually to ensure there are no light yellow lumps or filamentous substances; then continue to mix at medium speed for 40 minutes to ensure uniform mixing of the materials.

[0191] Mixing Reference Example Weigh 40 g of sodium carboxymethylcellulose (viscosity 3000 - 4000 mPa·s, Type 9) and 360 g of drinking water into a planetary mixer, mix at low speed for 5 minutes, then continue to mix at medium speed for 20 minutes. Check visually to ensure there are no white lumps. Dissolve 1 g of chitosan oligosaccharide in 99 g of drinking water. Add 200 g of drinking water to the planetary mixer, mix at medium speed, and drip the chitosan oligosaccharide aqueous solution at a rate of 5 mL / min while mixing. Check visually during the dripping process to ensure there are no light yellow lumps or filamentous substances formed; wash the container of the chitosan oligosaccharide aqueous solution with a small amount of water multiple times, and make up the water to a total material mass of 800 g. Then continue to mix at medium speed for 40 minutes to ensure uniform mixing of the materials.

[0192] Mixing Comparative Example 1 Weigh 40 g of sodium carboxymethylcellulose (viscosity 3000 - 4000 mPa·s, Type 9) and 360 g of drinking water into a planetary mixer, mix at low speed for 5 minutes, then continue to mix at medium speed for 20 minutes. Check visually to ensure there are no white lumps. Dissolve 1 g of chitosan oligosaccharide and 0.25 g of potassium citrate in 50 g of drinking water. Add 200 g of drinking water to the planetary mixer, quickly pour in the composite aqueous solution of chitosan oligosaccharide and potassium citrate, wash the container of the composite aqueous solution with a small amount of water multiple times and pour it into the planetary mixer, and make up the water to a total material mass of 800 g. Mix at low speed for 5 minutes, check visually to find a large number of light yellow lumps and filamentous substances; then continue to mix at medium speed for 120 minutes, and check visually to find that there are still a small number of light yellow lumps.

[0193] Mixing Comparative Example 2 Weigh 40 g of sodium carboxymethylcellulose (viscosity 3000 - 4000 mPa·s, Type 9) and 360 g of drinking water into a planetary mixer, mix at low speed for 5 minutes, then continue to mix at medium speed for 20 minutes. Check visually to ensure there are no white lumps. Dissolve 1 g of chitosan oligosaccharide in 50 g of drinking water. Add 200 g of drinking water to the planetary mixer, quickly pour in the chitosan oligosaccharide aqueous solution, wash the container of the chitosan oligosaccharide aqueous solution with a small amount of water multiple times and pour it into the planetary mixer, and make up the water to a total material mass of 800 g. Mix at low speed for 5 minutes, check visually to find a large number of light yellow lumps and filamentous substances; then continue to mix at medium speed for 180 minutes, and check visually to find that there are still a small number of light yellow lumps.

[0194] The above mixing examples, reference examples and mixing comparative examples show that adding potassium citrate can effectively improve the mixing efficiency and simplify the mixing process.

[0195] The mixtures obtained from Mixing Examples 1 and 2 and the Mixing Reference Example were dispensed and spread out flat in a PP food-contact plastic box, and dried in a blast dryer at 80 °C for 20 hours; they were crushed and screened to obtain component particles with a size of 0.4 - 1 mm, and some of the particles were taken and placed in a stainless steel tray, and dried in a blast dryer at 80 °C, 95 °C, and 105 °C for 2 hours respectively. The above-obtained particles were used for subsequent swelling property tests.

[0196] Table 7 lists the liquid absorption multiples of the particles obtained from Mixing Examples 1 and 2 and Mixing Reference Example 1 after swelling in 1 / 10 diluted simulated gastric juice (pH = 2.5) for 1 hour:

[0197] Table 7

[0198] Sample Potassium citrate content +80℃2h +95℃2h +105℃2h Mixing Reference Example 1 0 76.0 84.0 66.4 Mixing Example 1 0.5 times 94.5 85.4 66.3 Mixing Example 2 1 times 93.2 88.7 69.5

[0199] The above results show that when the drying conditions are different, the effect of adding potassium citrate on the liquid absorption multiple will also change. It is speculated that on the one hand, adding a monovalent metal salt of an organic acid can weaken the aggregation between chitosan and chitosan, which is beneficial to the increase of crosslinking points, thereby reducing the liquid absorption multiple. On the other hand, adding a monovalent metal salt of an organic acid can weaken the cation-anion interaction between chitosan and sodium carboxymethylcellulose, which helps to reduce the crosslinking degree of the chitosan crosslinked polymer and increase the liquid absorption multiple. When it is in excess, it even destroys the crosslinking effect. And when these two effects reach an equilibrium and cancel each other out, such as when the secondary drying temperature is 95 °C, the effect on the liquid absorption multiple is not significant. At the same time, it also shows the complexity of the influence of the monovalent metal salt of an organic acid on crosslinking, which is also affected by other factors such as drying conditions and does not follow a single rule.

[0200] Table 8 lists the liquid absorption multiples of the particles obtained from Mixing Examples 1 and 2 and Mixing Reference Example 1 after secondary drying at 95 °C for 2 hours in 1 / 10 diluted simulated gastric juice (pH = 2.5) and simulated intestinal fluid (pH = 6.8), and the state of the particles after swelling and filtration in the simulated intestinal fluid:

[0201] Table 8

[0202] Sample Potassium citrate content pH = 2.5, 1 h pH = 2.5, 3 h pH = 6.8, 2 h Mixing Reference Example 1 0 84.0 81.9 10.2, complete dissociation Mixing Example 1 0.5 times 85.4 82.5 22.1, small amount of soft amorphous residue Mixing Example 2 1 times 88.7 85.3 13.5, complete dissociation

[0203] The above results show that by adjusting parameters such as the content of potassium citrate and drying conditions, it is also possible to achieve that adding potassium citrate only affects its processing performance without affecting its crosslinking degree, swelling multiple and dissociation performance.

[0204] Satiety effect comparison

[0205] In order to understand the absorption and retention of liquid by the said particles in the human digestive tract, the following research was carried out.

[0206] Three subjects were required to fast and refrain from drinking for 3 hours before a meal, and drink (1) solid beverage (1) and drinking water with a total amount of 400 mL of drinking water 0.5 hour before the meal; or (2) solid beverage (2) and drinking water with a total amount of 400 mL of drinking water; or (3) solid beverage (3) and drinking water with a total amount of 400 mL of drinking water; or (4) solid beverage (4) and drinking water with a total amount of 400 mL of drinking water; or (5) only drink 400 mL of drinking water. Each person's meal consisted of half a serving of rice (relative to each subject's daily food intake), one serving of meat, two servings of vegetables, and one serving of soup (about 250 mL). After the meal, fasting and water abstinence were maintained until the end of this round of research. The time periods and frequencies of urination were recorded after drinking water, and the satiety status was asked. Two rounds were conducted in total.

[0207] Among them, the screening criteria for the subjects were: fasting and water abstinence for 3 hours before the meal, drinking 400 mL of drinking water 0.5 hour before the meal, having normal meals, and urinating 3 times or more within 2.5 hours after drinking water.

[0208] The components of the solid beverage are as follows:

[0209] Food-grade superabsorbent particles 0.4 - 1 mm, 2.5 g;

[0210] Hydrolyzed collagen, 1 g;

[0211] White kidney bean extract, 1 g

[0212] Citric acid, 45 mg;

[0213] Neotame, 5 mg;

[0214] Natural fruit powder, 0.8 g.

[0215] Among them, the food-grade superabsorbent particles in solid beverage (1) were prepared according to the aforementioned mixing example 1, dried at 80 °C for 20 hours, and secondarily dried at 95 °C for 2 hours; the food-grade superabsorbent particles in solid beverage (2) were prepared according to the aforementioned mixing reference example 1, dried at 80 °C for 20 hours, and secondarily dried at 95 °C for 2 hours; the food-grade superabsorbent particles in solid beverage (3) were prepared according to the aforementioned reference example 3 - 1; the food-grade superabsorbent particles in solid beverage (4) were prepared according to the aforementioned example 8 - 1.

[0216] The number of urinations of the subjects who drank the solid beverages (I), (II), and (IV) before meals decreased from 3 times or more within 2.5 hours to 1 - 2 times, and the initial urination time was significantly delayed by 0.5 - 1 hour. However, there was no significant difference in the number of urinations of the subjects who drank the solid beverage (III) and those who only drank water. By statistically analyzing the relatively concentrated urination periods of the subjects, it can be summarized that the particles have a certain retention effect on the liquid in the digestive tract, and then the particles dissociate to release water, which is manifested as an increase in the number of urinations. Correspondingly, the satiety of the subjects who drank the solid beverages (I), (II), and (IV) before meals was postponed from about 3 hours without drinking the solid beverage to about 5 hours, while the extension of satiety was not significant for the subjects who drank the solid beverage (III) before meals.

[0217] The above are only embodiments of the present invention, and do not limit the patent scope of the present invention accordingly. Any equivalent structure or equivalent process transformation made by using the content of the specification of the present invention, or directly or indirectly applied in other related technical fields, shall be equally included in the patent protection scope of the present invention.

Claims

1. A chitosan oligosaccharide cross-linked polymer, characterized in that, The chitosan cross-linked polymer described above contains at least chitosan, sodium carboxymethyl cellulose and a monovalent metal salt of organic acid. The chitosan cross-linked polymer is cross-linked at least by the physical interaction between the amino group in chitosan and the carboxyl group in sodium carboxymethyl cellulose. Among them, the content of chitosan is 1%-10% of the mass of sodium carboxymethyl cellulose, and the mass ratio of chitosan to the monovalent metal salt of organic acid is 1:0.1 to 1:

2.

2. The chitosan cross-linked polymer according to claim 1, wherein The degree of substitution of the sodium carboxymethyl cellulose described above is not less than 0.6, and the viscosity of the 1% aqueous solution prepared from the sodium carboxymethyl cellulose at 25 °C is 200-4000 mPa·s.

3. The chitosan oligosaccharide cross-linked polymer according to claim 1, characterized in that, Among the monovalent metal salts of organic acid described above, the organic acid is selected from one or more of citric acid, malic acid, gluconic acid, lactic acid, and the monovalent metal is selected from one or two of sodium and potassium.

4. The chitosan oligosaccharide cross-linked polymer according to claim 1, wherein After adding the monovalent metal salt of organic acid, the liquid absorption multiple of the obtained chitosan cross-linked polymer after swelling in 1 / 10 diluted simulated gastric juice at pH = 2.5 for 1 hour is increased by at least 10%.

5. The chitosan oligosaccharide cross-linked polymer according to claim 1, wherein After adding the monovalent metal salt of organic acid, the liquid absorption multiple of the obtained chitosan cross-linked polymer after swelling in 1 / 10 diluted simulated gastric juice at pH = 2.5 for 1 hour is decreased by at least 10%.

6. The chitosan oligosaccharide cross-linked polymer according to claim 1, wherein After adding the monovalent metal salt of organic acid, the change in the liquid absorption multiple of the obtained chitosan cross-linked polymer after swelling in 1 / 10 diluted simulated gastric juice at pH = 2.5 for 1 hour is less than ±5%.

7. A food-grade superabsorbent particle, characterized in that, The food-grade superabsorbent particles contain a chitosan cross-linked polymer. The chitosan cross-linked polymer contains at least chitosan, sodium carboxymethyl cellulose and a monovalent metal salt of organic acid. The chitosan cross-linked polymer is cross-linked at least by the physical interaction between the amino group in chitosan and the carboxyl group in sodium carboxymethyl cellulose. Among them, the degree of substitution of the sodium carboxymethyl cellulose is not less than 0.6, and the viscosity of the 1% aqueous solution prepared from the sodium carboxymethyl cellulose at 25 °C is 200-4000 mPa·s. Among them, the content of chitosan is 1%-10% of the mass of sodium carboxymethyl cellulose, and the mass ratio of chitosan to the monovalent metal salt of organic acid is 1:0.1 to 1:

2. The food-grade superabsorbent particles contain or do not contain other food additives and do not contain a cross-linking agent that forms a chemical cross-link or a strong physical cross-link with any raw material. The food-grade superabsorbent particles have a liquid absorption multiple of not less than 50 times after swelling in 1 / 10 diluted simulated gastric juice at pH = 2.5 for 1-3 hours, and the change in the liquid absorption multiple after swelling for 3 hours compared with that after swelling for 1 hour does not exceed ±25%. After swelling in simulated intestinal fluid for 2 hours, they are completely dissociated or the swelling residue no longer maintains a granular state.

8. A food-grade superabsorbent particle according to claim 7, wherein, The particle size of the food-grade superabsorbent particles is 0.1-1 mm.

9. A product that provides efficient satiety, characterized in that, The product described above contains 0.1%-99.9% of the food-grade superabsorbent particles as described in claims 4-8 by mass.

10. A product for providing high - efficiency satiety according to claim 9, characterized in that, The product is a food, a drug or a medical device; the form of the food is a solid beverage, a candy, a pet food; the form of the drug or the medical device is a tablet, a capsule, a granule.

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